CN110176573A - A kind of modification method of lithium ion cell electrode production - Google Patents
A kind of modification method of lithium ion cell electrode production Download PDFInfo
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- CN110176573A CN110176573A CN201910349503.2A CN201910349503A CN110176573A CN 110176573 A CN110176573 A CN 110176573A CN 201910349503 A CN201910349503 A CN 201910349503A CN 110176573 A CN110176573 A CN 110176573A
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- activity compound
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0433—Molding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of modification method of lithium ion cell electrode production, preparation, collector pretreatment, the pretreatment of electrode activity compound, variable area densification and batch electrode fabrication including electrode activity compound.The present invention is on the basis of the existing Fabrication Technology of Electrode suitable for aqueous solution, without evading physics pressing step, electrode after improvement efficiently adapts to the Cyclic voltamogram characterization of lithium insert material, the cyclic voltammetry curve appearance of acquisition is narrow and sharp, peak type is undistorted, background area electric current is small, and can overcome the current noise caused by content is not low and the active layer densification uniformity is not high enough of electrode polarization, unit area active material.
Description
Technical field
The present invention relates to technical field of lithium ion, specifically a kind of aquo-lithium ion electricity with high stability
The production method of pond electrode.
Background technique
Lithium ion battery is because having the unapproachable energy density of in the past similar most of Rechargeable battery systems and function
Rate density can realize the purpose of short time fast charging and discharging while promoting system cruising ability.Currently, lithium ion battery
With mobile phone, laptop is in the modern digital product of representative using relatively broad.It is each for lithium-ion energy storage system
Secondary charge and discharge mean primary transfer and storage of the equivalent lithium ion charge by electrolyte between positive and negative electrode, electrode activity
The difference of material storage lithium mechanism determines the difference of system stored energy capacitance.Lithium ion battery exactly uses lithium insert material conduct
Lithium source is just endowed biggish rated capacity, this can not be accomplished using electric double layer capacitance and fake capacitance two dimension lithium storage materials
's.However, since the redox reaction occurred in electrolyte and lithium insert material interactive process is related to material surface simultaneously
Neighbouring atomic layer and deep layer body phase, so that the deintercalation of lithium ion actually contains the multi-level phase change of material, for example, cathode metal
Oxide type lithium insert material is undergoing the phase transformation generated when charge and discharge, in different phases cationic arrangement mode there is difference,
Cause the lithium deintercalation current potential based on some phase that can also change, reflecting the diffusion of material internal lithium and transporting there may be not
Together.Therefore, when studying a kind of lithium insert material, its electrochemical behavior is characterized as essential one using cyclic voltammetry
Step, it can provide important information for follow-up study.In effective cyclic voltammetry curve, peak position corresponding to redox reaction
Should be easy discrimination, it is necessary to the background area electric current in addition to peak position is small as far as possible so that sufficiently highlight peak type,
In this way, the peak type of lithium deintercalation reaction (cell type) be it is narrow and sharp, fake capacitance reaction in surface is then wide and blunt.Excellent electrode
Manufacture craft determines the performance of material electrochemical behavior.Existing lithium-ion battery system is using the electrolysis of organic and two class of water system
Liquid, the former is mainly that commercial Li-ion batteries (conventional lithium ion battery) uses, and is adapted to the electrode system of organic solvent accordingly
It is also very mature to make technique, reviews aquo-lithium ion battery, since electrolyte is aqueous solution, traditional Fabrication Technology of Electrode is difficult
Meet the electrochemical behavior characterization of material, problem is mainly reflected on the selection differences of binder and collector, is different from biography
System technique now preferentially uses PTFE (polytetrafluoroethylene (PTFE)) and stainless (steel) wire for the non-oily and special chemical activity of aqueous solution
Respectively as binder and collector.And PTFE is subjected to fibrosis ability toughness, nanoscale PTFE three-dimensional fiber web frame
Complex by lithium insert material and the formation of conductive agent physically encapsulation is the microscopic nature of source/drain, in most cases electrode
The final step of production is that complex and stainless (steel) wire physics are pressed.Generally speaking, electric current from collector to lithium by being embedded in
Several physical contact points are necessarily crossed over when the path of material, in the lithium insert material electrochemical behavior information finally obtained in this way
The noise contributions such as electrode polarization are necessarily contained, affect the subsequent judgement of researcher to a certain extent.On the other hand, must also
It should be noted that the electrode method that general production is suitable for aqueous solution is the electrode activity compound once to shape and to clean
The direct physics pressing of stainless (steel) wire, the electrode so prepared only can satisfy the test (cyclicity to lithium insert material performance
It is forthright again), and it is not suitable with electrochemical behavior characterization (cyclic voltammetry), using constant current as excitation, lithium is embedding for performance test
Enter the current potential of material as feedback, there is no limit thus have time enough to portray the overall picture of potential change, only in time
The differential capacity curve that correspondingly make constant current charge-discharge curve can be between intermediate description material phase transformation and current potential tendency
Relationship, however this indirect relation is based on derived from constant current, and the result of this and cyclic voltammetry is different because with
Feedback current is variation when Step potential is as excitation, contains the interactive information between electrode and electrolyte；Not only
In this way, the presence of scanning speed also limits the testing time, it is meant that going for effective cyclic voltammetry curve must just control
The content of electrode unit area active material processed so that it is enough it is low to guarantee current potential inswept phase transformation current potential near zone when
Corresponding redox reaction carries out completely；The kinetics difference of various lithium insert materials determines the speed of reaction, changes
Speech be exactly removal lithium embedded speed difference, the lithium insert material relatively blunt for kinetics, making use of momentum must ask more
Excellent Fabrication Technology of Electrode, and generally make and be difficult to decrease electrode unit area activity material suitable for the electrode method of aqueous solution
The content of material, the active layer densification uniformity is not high enough to cause electrode only to adapt to the faster lithium insert material of kinetics reluctantly
Electrochemical behavior characterization.And Y.G.Wang (Y.G.Wang, J.Y.Luo, C.X.Wang, Y.Y.Xia, Hybrid Aqueous
Energy Storage Cells Using Activated Carbon and Lithium-Ion Intercalated
Compounds, Journal of The Electrochemical Society, 153 (2006) A1425-A1431) speak of benefit
Evade the method bring unstability pressed using physics, with micro mist electrode (Micropowder Electrode) to adapt to
The demand of cyclic voltammetry environment, but the production needs of full electrode use glass tube, platinum filament, Gas blowtorch, polishing sand
Paper and chloroazotic acid, process is cumbersome, and excessive goods and materials are also expended while undertaking certain risk.
Summary of the invention
To solve the above problems, the present invention provides a kind of modification method of lithium ion cell electrode production, existing suitable
On the basis of the Fabrication Technology of Electrode of aqueous solution, this method is efficiently fitted without evading physics pressing step, the electrode after improvement
The Cyclic voltamogram of lithium insert material is answered to characterize, the cyclic voltammetry curve appearance of acquisition is narrow and sharp, and peak type is undistorted, background
Zone current is small, and can overcome electrode polarization, unit area active material content is not low and the active layer densification uniformity
Current noise caused by not high enough.
The present invention includes the preparation of electrode activity compound, collector pretreatment, the pretreatment of electrode activity compound, change face
Product densification and batch electrode fabrication, which is characterized in that the method comprises the following steps:
The preparation of S1, electrode activity compound: after dehydrated alcohol is added in PTFE dispersion emulsion, ultrasonic disperse is obtained
PTFE mixed liquor, stay in the PTFE mixed liquor can not observe obvious milky aggregate or precipitating when, stop ultrasound, will
It is stirred on the PTFE mixed liquor merging magnetic stirring apparatus, and conductive agent and electrode active material is added while stirring, it is close
It is honored as a queen and is persistently stirred overnight again, obtain slurry, then slurry is placed in water bath device, one side magnetic agitation heats water on one side
Water stops heating, the slurry of acquisition is placed on magnetic stirring apparatus to boiling to slurry to toothpaste-like in bath apparatus, with 30~
The revolving speed of 40r/s stirs, until slurry stops stirring, finally dry slurry, is i.e. acquisition electrode activity compound to butyrous
And it is collected in spare in sample box；
S2, collector pretreatment: collector is placed in clean No.1 mold, and physics pressure maintaining, by the collection after pressure maintaining
Fluid acetone and dehydrated alcohol are spare after being cleaned by ultrasonic and dry up respectively；
S3, the pretreatment of electrode activity compound: the electrode activity compound for taking step S1 to obtain is placed in No. two molds, and
Physics pressure maintaining obtains electrode activity compound thin slice；
S4, variable area densification: it is cut with the electrode activity compound thin slice that clean blade obtains step S3
It is more parts, a copy of it is taken to be placed on clean, smooth die surface, and is rolled with clean smooth clava and be depressed into thin slice area
It is not further added by, scoops up the thin slice because of pressure adsorption in die surface with the piece sword of razor blade, repeat this step is more than three times
It can get the electrode activity compound ultra-thin foil of surfacing and body phase densification；
S5, batch electrode fabrication: the step S4 ultra-thin foil obtained is cut into multi-disc with clean blade and is surpassed with batch
Thin laminae neatly arranges the same batch ultra-thin foil on same collector, and will be described same with physics laminating type
Batch ultra-thin foil fit in it is unlikely on collector fall off, the collector with the same batch ultra-thin foil is put in clean
In No.1 mold, physics pressure maintaining is carried out, collector is cut in the gap after the completion of pressure maintaining again between the compound object area of electrode activity
At multi-disc, and trim extra exposed collector corner.
Further, the No.1 mold in step S2 and S5 is the circular die that two panels diameter is 2~2.5cm,
No. two molds in step S3 are the tee T molds that internal diameter is 10~20mm, and the surface of the No.1 and No. two molds is
The material of polished surface, the No.1 and No. two molds is hard metal.
Still further, physics pressure maintaining described in step S2, S3 and S5 is to carry out pressure maintaining, the pressure of pressure maintaining with powder compressing machine
Size is 10~20MPa, and the dwell time is 1~6min.
Also further, the electrode activity compound weight in step S3 is 30~50mg.
Further, physics laminating type described in step S5 refer to roll pressure using clean smooth clava will be described
Unlikely fall off is bonded with collector with batch ultra-thin foil.
Further, in step S2, duration that collector acetone and dehydrated alcohol after pressure maintaining are cleaned by ultrasonic respectively
For 15min.
Further, PTFE is 60wt% in step S1, in PTFE dispersion emulsion, and is mixed in every 1gPTFE dispersion emulsion
50~200ml dehydrated alcohol is closed, the ultrasonic disperse time is 30~45min, and changes water one every 15min during ultrasonic disperse
Secondary, the conductive agent is acetylene black, and the electrode active material is intercalation materials of li ions, the use of the electrode active material and conductive agent
Amount, according to electrode active material: conductive agent: the mass ratio that PTFE mixed liquor is 15:3:2 calculates.
Further, in step S2 and S5, the collector is 304 stainless (steel) wires that mesh number is not less than 400；Step S5
In the blade be razor blade, the clava material be agate or hard metal.
Further, in the step S4, the electrode activity compound thin slice that step S3 is obtained is cut to 4 parts.
Further, in the step S5, the ultra-thin foil that step S4 is obtained be cut to it is small for 3mm × 3mm or
The square piece of person 2mm × 2mm.
The beneficial effects of the present invention are: the modification method that this patent proposes, is not changing current electrode technique --- electricity
Pole activated complex and clean stainless (steel) wire physics press --- in the case where, the efficient adjusted drainage circulation volt of the electrode of production
Peace test environment, essentially eliminates by generally making suitable for the electrode method bring electrode polarization of aqueous solution, unit area
Current noise caused by the content of active material is not low and the active layer densification uniformity is not high enough can be good at embodying electrode
Interaction scenario between electrolyte, and the electrochemical behavior of the lithium insert material relatively blunt for Chemical Kinetics
It also can efficient identification；In addition, operating process is simpler practical compared to micro mist electrode, Cyclic voltamogram characterizes validity
It is higher, stablize and is suitable within 5mV/s for the cyclic voltammetric table of conventional or unconventional (being greater than 1mV/s) of lithium insert material
Sign.
Detailed description of the invention
Fig. 1 is the commodity LiCoO of MTI- Ke Jing group production2Particle SEM photograph.
Fig. 2 is self-control spherical shape LiCoO2Particle SEM photograph.
Fig. 3 is the preceding 5 circle cyclic voltammetry curve of the MTI-LCO electrode of modification method production, and electrolyte is the 0.5M of pH=7
Li2SO4Solution, sweep speed 1mV/s.
Fig. 4 is the preceding 5 circle cyclic voltammetry curve of the MTI-LCO electrode of conventional method production, and electrolyte is the 0.5M of pH=7
Li2SO4Solution, sweep speed 1mV/s.
Fig. 5 is the preceding 5 circle cyclic voltammetry curve of the SPH-LCO electrode of modification method production, and electrolyte is the 0.5M of pH=7
Li2SO4Solution, sweep speed 1mV/s.
Fig. 6 is the preceding 5 circle cyclic voltammetry curve of the SPH-LCO electrode of conventional method production, and electrolyte is the 0.5M of pH=7
Li2SO4Solution, sweep speed 1mV/s.
Fig. 7 is self-control octahedron LiMn2O4Particle SEM photograph.
Fig. 8 is the preceding 5 circle cyclic voltammetry curve of the OCT-LMO electrode of conventional method production, and electrolyte is the 0.5M of pH=7
Li2SO4Solution, sweep speed 1mV/s.
Fig. 9 is the preceding 5 circle cyclic voltammetry curve of the SPH-LCO electrode of conventional method production, and electrolyte is pH=11's
0.5M Li2SO4Solution, sweep speed 1mV/s.
Figure 10 is the preceding 5 circle cyclic voltammetry curve of the SPH-LCO electrode of modification method production, and electrolyte is pH=11's
0.5M Li2SO4Solution, sweep speed 1mV/s.
Figure 11 is the preceding 3 circle cyclic voltammetry curve of the SPH-LCO electrode of modification method production, and electrolyte is pH=7's
0.5M Li2SO4Solution, sweep speed 5mV/s.
Specific embodiment
In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment and join
According to attached drawing, the present invention is described in more detail.It should be understood that these descriptions are merely illustrative, and it is not intended to limit this hair
Bright range.In addition, in the following description, descriptions of well-known structures and technologies are omitted, to avoid this is unnecessarily obscured
The concept of invention.
Embodiment 1:
I. the preparation of the MTI-LCO electrode activity compound of modification method production:
The dispersion of S1, PTFE: 0.0445g PTFE dispersion emulsion, 20ml dehydrated alcohol are weighed respectively, first disperses PTFE
Lotion is placed in beaker, then dehydrated alcohol is instilled in the beaker equipped with PTFE dispersion emulsion with dropper, meanwhile, beaker is shaken,
So that dehydrated alcohol enters demulsification to PTFE dispersion emulsion, then with preservative film by after the sealing of beaker mouth, ultrasonic disperse 35min is
Prevent water temperature in ultrasonic machine from overheating, every 15min changes a water, is uniformly dispersed and can not observe obvious milky white to solution in beaker
When color aggregate or precipitating, PTFE dispersion is completed；
S2, mixed slurry: PTFE scattered in step S1 is placed in magnetic stirrer together with beaker, while to burning
0.20025g commodity LiCoO is added one by one in cup2, 0.04005 acetylene black, then with preservative film close beaker, be persistently stirred overnight；
S3, slurry thickening: it by the beaker merging water bath device equipped with slurry by step S2 processing, opens on beaker
The preservative film of sealing, is slowly stirred, meanwhile, so that water is heated to boiling in water bath device, (institute is evaporated to dehydrated alcohol in beaker
Stating dehydrated alcohol is added dehydrated alcohol in step S1), slurry becomes thick therewith, until stop heating in toothpaste-like,
Beaker is taken out, is again sealed beaker with preservative film, thickening terminates at this time；
S4, PTFE fiber: the step S3 slurry obtained is placed on magnetic stirring apparatus, is stirred with the revolving speed of 40r/s, directly
To slurry to butyrous, stop stirring, PTFE fiberization is completed；
S5, the preparation of electrode activity compound: slurry prepared by step S4 is dried, that is, is obtained electrode activity compound and received
It combines in spare in sample box, electrode activity compound is set as MTI-LCO.
S6, collector pretreatment: the collector of 400 mesh, 304 stainless (steel) wire is taken to be placed in the cleaning circle that two panels diameter is 2cm
Between shape mold, and with powder compressing machine pressure maintaining, pressure size 10MPa, dwell time 1min, by the collector after pressure maintaining
It is spare after being cleaned by ultrasonic 15min respectively with acetone and dehydrated alcohol and dried up；
S7, the pretreatment of electrode activity compound: it takes the electrode activity compound obtained in 30mg step S5 to be placed in internal diameter to be
In the tee T mold of 13mm, and with powder compressing machine pressure maintaining, pressure size 10MPa, dwell time 1min obtain electrode
Activated complex thin slice；
S8, variable area densification: with clean razor blade that the electrode activity compound obtained in step S7 is thin
Piece is cut to four parts, and a copy of it is taken to be placed on clean mold plane, and is rolled with clean smooth clava and be depressed into thin slice area
It is not further added by, scoops up the thin slice because of pressure adsorption in die surface with the piece sword of razor blade, repeat to can be obtained for this step 3 times
The electrode activity compound ultra-thin foil of surfacing and body phase densification；
S9, batch electrode fabrication: if cutting the ultra-thin foil obtained in step S8 into same batch with clean razor blade
The square piece of dry 3mm × 3mm, they are neatly arranged on same collector, and roll pressure with clean smooth clava, until
The same batch ultra-thin foil be bonded with collector it is unlikely fall off, will be put in the collector with batch ultra-thin foil two pieces it is straight
Diameter is between the clean circular die of 2cm, and with powder compressing machine pressure maintaining, pressure size 10MPa, and the dwell time is
1min, collector finally is cut off by electrode activity compound region, and after trimming extra exposed collector corner, change
The MTI-LCO electrode fabrication of good recipe method production finishes.
II. the preparation of the SPH-LCO electrode activity compound of modification method production:
Step is consistent with preparing for MTI-LCO electrode, in addition to the slurry being added in S2 is that acetylene black and self-control are spherical
LiCoO2The slurry of (CN107572600A, on January 12nd, 2018 are open), the electrode activity compound that step S5 is obtained are set as
SPH-LCO, final S9 obtain the SPH-LCO electrode of modification method production.
Embodiment 2:
I. the preparation of the MTI-LCO electrode activity compound of conventional method production:
The dispersion of S1, PTFE: 0.0445g PTFE dispersion emulsion, 20ml dehydrated alcohol are weighed respectively, first disperses PTFE
Lotion is placed in beaker, then dehydrated alcohol is instilled in the beaker equipped with PTFE dispersion emulsion with dropper, meanwhile, beaker is shaken,
So that dehydrated alcohol enters demulsification to PTFE dispersion emulsion, then with preservative film by after the sealing of beaker mouth, ultrasonic disperse 35min is
Prevent water temperature in ultrasonic machine from overheating, every 15min changes a water, is uniformly dispersed and can not observe obvious milky white to solution in beaker
When color aggregate or precipitating, PTFE dispersion is completed；
S2, mixed slurry: PTFE scattered in step S1 is placed in magnetic stirrer together with beaker, while to burning
0.20025g commodity LiCoO is added one by one in cup2, 0.04005 acetylene black, then with preservative film close beaker, be persistently stirred overnight；
S3, slurry thickening: it by the beaker merging water bath device equipped with slurry by step S2 processing, opens on beaker
The preservative film of sealing, is slowly stirred, meanwhile, so that water is heated to boiling in water bath device, (institute is evaporated to dehydrated alcohol in beaker
Stating dehydrated alcohol is added dehydrated alcohol in step S1), slurry becomes thick therewith, until stop heating in toothpaste-like,
Beaker is taken out, is again sealed beaker with preservative film, thickening terminates at this time；
S4, PTFE fiber: the step S3 slurry obtained is placed on magnetic stirring apparatus, is stirred with the revolving speed of 40r/s, directly
To slurry to butyrous, stop stirring, PTFE fiberization is completed；
S5, the preparation of electrode activity compound: slurry prepared by step S4 is dried, that is, is obtained electrode activity compound and received
It combines in spare in sample box, takes electrode mixing 30mg, rotary push sizing is carried out to electrode mixing with the metal grinding tool of polishing, to
Observe that the electrode mixing sheet surface being formed in grinding tool slot is smooth spare without electrode mixing thin slice is taken out after obvious slight crack；It can be
The side that electrode mixing thin slice is contacted with metal grinding tool slot bottom is known as thin slice reverse side, otherwise is front, by electrode mixing thin slice
It is placed in clean polishing metal plane and thin slice face down, then collector is placed on thin slice reverse side, is equally being collected
Thin slice reverse side is squeezed into the pressure of 10MPa vertically downward using the polishing metal plane of a clean surface above fluid netted
In collector, the collector for being loaded with electrode mixing is taken out after pressure maintaining 1min, (the curved interior angle of collector is bending collector at this time
145 °) whether observation electrode mixing engages closely, if electrode mixing edges of regions is without departing from collector and electrode mixing front oil
Light is sliding, the collector for being loaded with electrode mixing is taken out, then 60 DEG C of dry 2h, the MTI-LCO electrode fabrication of conventional method production
It completes.
II. the preparation of the SPH-LCO electrode activity compound of conventional method production:
Step is consistent with preparing for MTI-LCO electrode, in addition to the slurry being added in S2 is that acetylene black and self-control are spherical
LiCoO2The slurry of (CN107572600A, on January 12nd, 2018 are open), the electrode activity compound that step S5 is obtained are set as
SPH-LCO, final S9 obtain the SPH-LCO electrode of modification method production.
Fig. 1 and 2 characterizes commercial and self-control spherical shape LiCoO respectively2The microscopic appearance of particle, main region of the latter compared with the former
It is not that it belongs to secondary spherical particle, body mutually has crystal boundary.In order to study various granule-morphology for respective electrochemical behavior
Influence, we have investigated two kinds of materials in the 0.5M Li of pH=7 using cyclic voltammetry2SO4Lithium deintercalation situation in solution,
And modification method and general production is respectively adopted and has made electrode suitable for the electrode method of aqueous solution.It can be bright from Fig. 3~6
The aobvious difference and rule found out MTI-LCO the and SPH-LCO electrode using modification method production and can more highlight two kinds of materials, is compared
For MTI-LCO the and SPH-LCO electrode of conventional method production, appearance is narrow and sharp, and peak type is undistorted, background area electric current
It is small.So as to learn commercial LiCoO by Fig. 3 and 52A pair of of redox peaks can be only shown, there is excellent capacity
Utilization rate almost can achieve 100% below 0.85V vs SCE, and such be advantageous in that can be to avoid LiCoO2Stratiform is brilliant
Body cyclicity caused by undergoing irreversible structure to crumble under crossing high potential deteriorates and capacity attenuation, and spherical shape LiCoO2Performance
Go out three pairs of redox peaks, corresponds to the structural phase transition three times during removal lithium embedded.In addition, Fig. 3 and 5 is it can be observed that peak
It is worth electric current with the decaying of circle number, this is because LiCoO2Proton insertion effect can occur in neutral aqueous solution for layer structure, should
Effect is irreversible to will lead to capacity attenuation.
Embodiment 3:
I. the preparation of the OCT-LMO electrode activity compound of conventional method production:
The step S1 mono- of S1 and the preparation method of the MTI-LCO electrode activity compound of conventional method production in embodiment 2
It causes
S2, mixed slurry: PTFE scattered in step S1 is placed in magnetic stirrer together with beaker, while to burning
0.36994g self-control octahedron LiMn is added in cup one by one2O4(GuanhuaJin, HangQiao, HualinXie,
HaiyanWang, KejianHe, PingLiu, JiajieChen, YougenTang, SuqinLiu, ChenghuanHuang,
Synthesis of single-crystalline octahedral LiMn2O4as high performance cathode
For Li-ion battery, Electrochimica Acta, Volume 150,20December 2014, Pages 1-7),
0.04005 acetylene black, then beaker is closed with preservative film, it is persistently stirred overnight, obtains slurry；
Step S3~S5 mono- of the preparation method of S3~S5 and the MTI-LCO electrode activity compound of conventional method production
It causes, the OCT-LMO electrode fabrication of conventional method production is completed.
II. the preparation of the SPH-LCO electrode activity compound of conventional method production:
It is consistent with the preparation method of SPH-LCO electrode that conventional method in embodiment 2 makes.
III. the preparation of the SPH-LCO electrode activity compound of modification method production:
It is consistent with the preparation method of SPH-LCO electrode that modification method in embodiment 1 makes
Fig. 2 and 7 characterizes LiCoO respectively2And LiMn2O4The microscopic appearance of powder sample.LiMn2O4Particle is ideal eight
Face body, this is identical as commercial style.Secondary spherical particle (partial size is less than 7 μm) not of uniform size can make LiCoO2Powder have compared with
High bulk density and low degree of aggregation --- because on the one hand there was only the contact area of ball and ball in all geometrical contact models
Be it is the smallest, on the other hand ball not of uniform size in unit volume is bigger more than the ball compactedness that partial size is all 7 μm --- from
And the ohmic polarization of electrode SPH-LCO active layer can be reduced as far as possible.From Fig. 8 and 9 as can be seen that conventional method made
OCT-LMO electrode is only able to satisfy LiMn2O4Cyclic voltammetry, conventional method production SPH-LCO be but not applied for
LiCoO2Although reducing the ohmic polarization of SPH-LCO as far as possible, this is primarily due in Li2SO4LiMn in solution2O4Have
Compare LiCoO2Faster kinetics, therefore general production is suitable for the electrode method of aqueous solution it is enough.Utilize improvement side
The SPH-LCO electrode of method production is tested (Figure 10), it is found that the peak type distortion and peak fusion phenomenon in original Fig. 9 have disappeared
It loses, appearance is more sharp and narrow, and background area electric current is substantially reduced, and efficiently features spherical LiCoO2Electrochemical scholarship and moral conduct
For.In addition, because LiMn2O4It is not influenced by pH value of solution, for formed comparison, LiCoO2It must be maintained at pH=11's
Proton insertion effect can just be evaded by, which testing in solution, is unlikely to cause penalty.
Embodiment 4:
The preparation of the SPH-LCO electrode activity compound of modification method production:
The step of preparation method for the SPH-LCO electrode activity compound that S1~S5 makes with modification method in embodiment 1
S1~S5 is consistent
S6, collector pretreatment: the collector of 400 mesh, 304 stainless (steel) wire is taken to be placed in the cleaning circle that two panels diameter is 2cm
Between shape mold, and with powder compressing machine pressure maintaining, pressure size 12MPa, dwell time 1min, by the collector after pressure maintaining
It is spare after being cleaned by ultrasonic 15min respectively with acetone and dehydrated alcohol and dried up；
S7, the pretreatment of electrode activity compound: it takes the electrode activity compound obtained in 30mg step S5 to be placed in internal diameter to be
In the tee T mold of 13mm, and with powder compressing machine pressure maintaining, pressure size 10MPa, dwell time 1min obtain electrode
Activated complex thin slice；
S8, variable area densification: with clean razor blade that the electrode activity compound obtained in step S7 is thin
Piece is cut to four parts, and a copy of it is taken to be placed on clean mold plane, and is rolled with clean smooth clava and be depressed into thin slice area
It is not further added by, scoops up the thin slice because of pressure adsorption in die surface with the piece sword of razor blade, repeat to can be obtained for this step 7 times
The electrode activity compound ultra-thin foil of surfacing and body phase densification；
S9, batch electrode fabrication: if cutting the ultra-thin foil obtained in step S8 into same batch with clean razor blade
The square piece of dry 2mm × 2mm, they are neatly arranged on same collector, and roll pressure with clean smooth clava, until
The same batch ultra-thin foil be bonded with collector it is unlikely fall off, will be put in the collector with batch ultra-thin foil two pieces it is straight
Diameter is between the clean circular die of 2cm, and with powder compressing machine pressure maintaining, pressure size 12MPa, and the dwell time is
1min, collector finally is cut off by electrode activity compound region, and after trimming extra exposed collector corner, change
The SPH-LCO electrode fabrication of good recipe method production finishes.
Figure 11 describes 0.5M Li of the SPH-LCO electrode in pH=7 of modification method production2SO4Preceding 3 measured in solution
Enclose cyclic voltammetry curve.Entirety is made a general survey of, curve appearance is narrow sharp, and background area electric current is increased slightly, this is primarily due to adopt
With the 5mV/s for being higher than normal condition (sweep speed for the cyclic voltammetry of lithium insert material and be usually less than 1mV/s), but it is different
The changing rule enclosed between curve is obvious, illustrates electrode stability height.Review Y.G.Wang (Y.G.Wang, J.Y.Luo,
C.X.Wang,Y.Y.Xia,Hybrid Aqueous Energy Storage Cells Using Activated Carbon
and Lithium-Ion Intercalated Compounds,Journal of The Electrochemical
Society, 153 (2006) A1425-A1431) utilize micro mist electrode 1M Li at 10mV/s2SO4Test result in solution,
Although 10mV/s lower curve background area electric current very little, this can only illustrate the LiCoO of electrode2Content it is very low, but from first three circle
The mixed and disorderly variation of curve can be seen that electrode stability is not high, be only capable of probably knowing that material receives the shadow of proton insertion effect
It rings, can not qualitatively find out specific rule from the variation of peak point current and spike potential as Figure 11.In addition, 10mV/s
It is not very necessary, because the peak point current measured in 1mV/s is normalized into multiplying power (C system for lithium insert material
Degree, the ratio electric current that 1C is and rated capacity numerical values recited is equal) when, often already exceed the feature work electric current of lithium ion battery
Multiplying power.
It should be understood that above-mentioned specific embodiment of the invention is used only for exemplary illustration or explains of the invention
Principle, but not to limit the present invention.Therefore, that is done without departing from the spirit and scope of the present invention is any
Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.In addition, appended claims purport of the present invention
Covering the whole variations fallen into attached claim scope and boundary or this range and the equivalent form on boundary and is repairing
Change example.
Claims (8)
1. a kind of modification method of lithium ion cell electrode production, which is characterized in that preparation, collection including electrode activity compound
Fluid pretreatment, the pretreatment of electrode activity compound, variable area densification and batch electrode fabrication, the method step is such as
Under:
The preparation of S1, electrode activity compound: after dehydrated alcohol is added in PTFE dispersion emulsion, ultrasonic disperse obtains PTFE
Mixed liquor stays in the PTFE mixed liquor when can not observe obvious milky aggregate or precipitating, stops ultrasound, will be described
It is stirred on PTFE mixed liquor merging magnetic stirring apparatus, and conductive agent and electrode active material is added while stirring, after sealing
It is persistently stirred overnight again, obtains slurry, then slurry is placed in water bath device, one side magnetic agitation, one side heated water bath dress
Interior water is set to boiling, stops heating to slurry to toothpaste-like, the slurry of acquisition is placed on magnetic stirring apparatus, with 30~40r/s
Revolving speed stirring acquisition electrode activity compound and receive until slurry to butyrous, stops stirring, finally dries slurry
It combines in spare in sample box；
S2, collector pretreatment: collector is placed in clean No.1 mold, and physics pressure maintaining, by the collector after pressure maintaining
It is spare after being cleaned by ultrasonic and dried up respectively with acetone and dehydrated alcohol；
S3, the pretreatment of electrode activity compound: the electrode activity compound for taking step S1 to obtain is placed in No. two molds, and physics
Pressure maintaining obtains electrode activity compound thin slice；
S4, variable area densification: the electrode activity compound thin slice that step S3 is obtained is cut to clean blade more
Part, take a copy of it to be placed on clean, smooth die surface, and roll with clean smooth clava and be depressed into thin slice area no longer
Increase, scoop up the thin slice because of pressure adsorption in die surface with the piece sword of clean blade, repeating this step can obtain more than three times
Obtain the electrode activity compound ultra-thin foil of surfacing and body phase densification；
S5, batch electrode fabrication: it is ultra-thin thin with batch that the step S4 ultra-thin foil obtained is cut into multi-disc with clean blade
Piece neatly arranges the same batch ultra-thin foil on same collector, and with physics laminating type by the same batch
Ultra-thin foil fit in it is unlikely on collector fall off, the collector with the same batch ultra-thin foil is put in clean No.1
In mold, carry out physics pressure maintaining, after the completion of pressure maintaining again the gap between the compound object area of electrode activity collector is cut into it is more
Piece, and trim extra exposed collector corner.
2. a kind of modification method of lithium ion cell electrode production according to claim 1, it is characterised in that: step S2 and
The No.1 mold in S5 is the circular die that two panels diameter is 2~2.5cm, and No. two molds in step S3 are interior
Diameter is the tee T mold of 10~20mm, and the surface of the No.1 and No. two molds is polished surface, the No.1 and No. two moulds
The material of tool is hard metal.
3. a kind of modification method of lithium ion cell electrode production according to claim 1, it is characterised in that: step S2,
Physics pressure maintaining described in S3 and S5 is that pressure maintaining is carried out with powder compressing machine, and the pressure size of pressure maintaining is 10~20MPa, and the dwell time is
1~6min.
4. a kind of modification method of lithium ion cell electrode production according to claim 1, it is characterised in that: in step S3
The electrode activity compound weight be 30~50mg.
5. a kind of modification method of lithium ion cell electrode production according to claim 1, it is characterised in that: in step S5
The physics laminating type refers to that rolling pressure using clean smooth clava is bonded the same batch ultra-thin foil with collector
It is unlikely to fall off.
6. a kind of modification method of lithium ion cell electrode production according to claim 1, it is characterised in that: step S2
In, when a length of 15min that collector acetone and dehydrated alcohol after pressure maintaining are cleaned by ultrasonic respectively.
7. a kind of modification method of lithium ion cell electrode production according to claim 1, it is characterised in that: step S1
In, PTFE is 60wt% in PTFE dispersion emulsion, and 50~200ml dehydrated alcohol is mixed in every 1gPTFE dispersion emulsion, ultrasound
Jitter time is 30~45min, and it is primary every 15min to change water during ultrasonic disperse, and the conductive agent is acetylene black, described
Electrode active material is intercalation materials of li ions, the dosage of the electrode active material and conductive agent, according to electrode active material: conductive
Agent: the mass ratio that PTFE mixed liquor is 15:3:2 calculates.
8. a kind of modification method of lithium ion cell electrode production according to claim 1, it is characterised in that: step S2 and
In S5, the collector is 304 stainless (steel) wires that mesh number is not less than 400；The blade in step S5 is razor blade, described
Clava material is agate or hard metal.
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